Azo dye and process of preparing same



Patented June 19, 1934 UNlTED STATES AZO DYE AND PROCESS OF PREPARINGSAME Henry Jordan and Miles Augustinus Dahlen, Wilmington, Del.,assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application September 19, 1931,Serial No. 563,898

Claims.

This invention relates to a novel class of monoazo dyes and theirpreparation. These dyes are especially adapted to dyeing acetylcellulose. We

, have found that valuable monoazo dyes useful in dyeing acetylcellulose can be prepared by coupling a diazo compound of the benzene ornaphthalene series which does not contain a ree sulfoor carboxy-group toan amine which possesses the following probable formula:

NHz

R2 being an alkyl group, X, Y, and Z being hydrogen, alkyl, alkoxy orhalogen.

The new dyes will most probably have the following general formula:

R1 meaning a radical of the benzene or naphthalene series not containinga free sulphoor carboxy-group, R2 meaning an alkyl group, and

X, Y and Z meaning hydrogen, alkyl, alkoxy or halogen.

In order to fully illustrate the new invention the following examplesmay be given;

Example I 93 parts of aniline are diazotized in the usual way. To thediazo solution there is added a solution of 123 parts of m-anisidine in2000 parts of water and 120 parts of a; 31% hydrochloric acid solution.The mineral acidity of the coupling is neutralized with sodium acetate,maintaining a slight mineral acid reaction on Congo red paper. Afterstirring over night at 10-15 C. the coupling will be finished. The dyeis salted out from an acid solution and dried. In its dry, ground formit represents a dark violet black powder. The new dye has most probablythe following formula:

On reduction with stannous chloride it will yield aniline and 25-diamino-anisol.

The new dye is soluble in acidified water (acids used may be a mineralacid or oxalic acid) with a bright yellowish orange coloration. Thesolution in concentrated sulphuric acid is of a bright yellowish orangecolor. The product will dye acetyl cellulose from an acid bath in bright(o1. 2ee 97) greenish yellow shades of a very good tinctorial power. Ondiazotizing on the fiber and developing with beta-naphthol a brightbluish scarlet is obtained; with resorcin a full orange-brown;- and withbeta-oxynaphthoic acid a deep bluish- Bordeaux. The dyeings are fast towashing and to light and will give a pure white with a proper reducingdischarge medium.

Example II If, in Example I, the 93 parts of anilineare substituted by107 parts of p-toluidine, leaving all other conditions the same, a dyeis obtained which in its dry, ground form is a reddish brown powdersoluble in acidified water with an orange coloration; in concentratedsulphuric acid with a reddish orange color. It will dye acetyl cellulosein bright yellow shades; the beta-naphthol developed shade isbluish-red; beta-oxy-naphthoic a reddish-violet. The properties aresimilar to those given in Example I. The dye most probably has thefollowing formula:

. OOH; yielding on reduction with stannous chloride ptoluidine and2:5-diamino-anisol.

Example III Substituting in Example I the 93 parts of aniline by 143parts of alpha-naphthylamine, leaving all other conditions the same, adye is obtained which in its dry, ground form is a dark brown powder,soluble in acidified water with an orange coloration; in concentratedsulphuric acid with a deep bluish violet coloration. It will dye acetylcellulose in orange shades, which when diazotized and developed withbeta-naphthol will give a Bordeaux; with resorcin a brown; and withbetaoxy-naphthoic acid a reddish-violet.

The dye most probably has the following formula:

It yields, on reduction with stannous chloride,

alpha-naphthylamine and 2 5-diamino-anisol.

The properties of this dye are similar to those of Example I.

Example IV Substituting in Example I, 120 parts of manisidine by 153parts of amino-hydroquinonedimethyl-ether, leaving all other conditionsthe same, the dye obtained represents in its dry, ground form anorange-red powder, soluble in acidified water with an orange coloration;in concentrated sulphuric. acid witha Bordeaux coloration. It'will dyeacetyl cellulose in bright yellowof Example I. This dye most probablyhas the following formula:

ish orange shades. The shades with various de- 0on3 velopers are asfollows:

Beta-naphthol bright bluish-violet I Resorcin Bordeaux 0 CHBeta-oxy-naphthoic aCidb1"ight blue 011 ght On reduction with stannouschloride it will yield dyeing b s aniline and 25-diaminohydroquinone-dimethylblack on heavy ether. dyeings. Othercombinations are given in tabular form The properties of the dyeings aresimilar to those in the following table.

Diazo compound Coupling compound Direct shade figgg Resorcin shade g gzz g0 pgtoluidine Amino-hydroquinone-di- Orange Bright reddish- MaroonBright blue to methyl-ether. violet. black. p-anisidineAmino-hydroquinonedi- Yellowish-brown Bright bluish-vio- Dullredd1sh-vio- Lightgreenishblue methyl-ether. 7 let. let. to black.p-phenetidine Arnino-hydroquinone-di- Yellowish-brown Bright bluish-vio-Dull reddish-vlo- Lightgreenlshblue methyLether. let. let. to black.Trace duller than panisidinedye. Alpha-naphthylamineAmingliydfioqninone-di- Yellowish-brown Bluish-violet Dill: reddish-v1o-Greenish-blue.

met y-et er. e. Beta-naphthylamine Amino-hydroquinone-di-Yellowisli-orange Bluish-violet Dull reddish-vio- Greenish-blue.methyl-ether. let. 7

. Amino-hydroquinone-di- Red Bluish-violet Reddish-violet Blue.

methyl-ether. Amino-hydroquinone-di- Reddish-yellow... Violet BordeauxBlue.

methyl-ether. Amino-hydroquinone-di- Bright orange VioletBluish-Bordeaux. Blue.

methyl-ether. Amino-hydroquinone-di- Orange... Violet ReddishvioletGreenish-blue. methyl-ether.

4-nitro-2-anisidine Amino-hydroquinone-di- Orange" Violet Reddishvi01et.Blue.

methyl-ether. p-chloroaniline Amino-hydroquinone-di- Orange VioletBordeaux Bright blue to methyl-ether. black. Acetyl-p-phenylenediamineAmirig-liydliioquinone-di- Orange-brown Bluish-violet Reddish-violet'Verygreenishblue.

' me y-e er. Acetyl m-toluylenediamine. A ino-hydroquinone-di- Lightorange Dull reddish-vio- Maroon Gray,

methyl-ether. let. o-anisidine Amlno-hydroqulnone-dl- Orange Dullreddish-vio- Dull Bordeauxun Gray.

methyl-ether. let. 5-nitro-2-anisidine Amino-hydroquinone-di- RedBluish-violet Reddish-violet.. ,Reddish gray.

methyl-ether. Oresidine Amino-hydroquinone-di Reddish-orange... Dullreddish-vio- Bordeaux Reddish gray.

methyl-ether. let. 4 Amino-hydroquinone-di- Amino-hydroquinone-di-Yellowish-brown Bluish-violet Dull violet Greenish blue. 11'5methyl-ether. methyl-ether. 3-nitro-4-anisidine Amino-hydroquinone-di-Dull red Dull reddish-vio- Dull'BordeauX Reddish-gray.

' methyl-ether 1 let; 1:7-amino-naphthol Amiitizg-ltllyrzfioquinonadi-Yellowish-brown-. Bluish-violet Reddish-vio1et Verygreenish-gray.

. me y-e er. Alpha-naphthylamine Arnilnti-hgldroquinone-di-Reddish-browm... Bluish-violet Reddisl1-violet Verygreenish-blue.

e y-e er. i-toluidine Amino-hydroquinone-di- Orange Violet Maroon Blue.

ethyl-ether. p -nitmaniline i2-ch1or-3-amino-anisol Orange Bluish-red0range-brown Bordeaux. p -anisidine 2-ch1or-3-amino-an1s0l.. OrangeBluish-red Orange-brown..." Violet.

FHs NH2Y Aniline Yellow Bright Bordeaux. Orange-brown. Violet.

NHz p-anisidine Orange-brown; Bluish-Bordeaux. Maroon: Reddish-blue.

I Alpha-naphthylamine Orange-broWn Dull Bordeaux Reddish-brown Navyblue.

OOH

In addition to the diazo compounds mentioned in the preceding examplesand in the foregoing table, other amino compounds of the benzene andnaphthalene series, which do not contain a free sulfoor carboxygroup,may be used. For example, the various halogenated anilines, toluidines,and anisidines, the nitro-aminoand halogenated nitro-amino-derivativesof the benzene and naphthalene series, and the aminobenzamides,amino-sulphonamides, and aminosulphonanilides may be used when in thediazotized condition.

Other coupling compounds which correspond to the general formula:

Y OR:

in which R2 is an alkyl group; X, Y, and Z may be hydrogen, alkyl,alkoxy or halogen may be employed, thus m-phenetidine,1-amino-3-methoxy- G-methylbenzene and various homologues of these andthe other illustrative compounds may be employed.

In general, these dyes show a very good solubility in an acid solutionand have exceptional afiinity for acetyl cellulose in an acid bath.Moreover, having a free amino group they may be diazotized and developedon the fiber, producing various shades of good fastness to washing andto light and giving a white discharge with reducing discharge media.

Since many embodiments of this invention, differing widely in one ormore respects, may be made without departing from the spirit of ourinvention, it is to be understood that we do not limit ourselves to theforegoing examples or description except as indicated in the followingclaims:

We claim:

1. A process for producing azo dyes which comprises coupling adiazotized amine of the benzene or naphthalene series which may havesubstituted thereon members selected from the groups consisting ofalkyl, alkoxy, nitro, and halogen, with an amine of the followinggeneral formula:

Y OR:

in which R2 is an alkyl group, and X, Y and Z are hydrogen, halogen,alkyl or alkoxy groups.

2. An azo dye having the following general formula:

mula:

(SCH:

in which R1 is an aromatic nucleus of the benzene series which may havesubstituted thereon members selected from the group consisting of alkyl,alkoxy, nitro and halogen.

5. .A process of preparing a dyestuif suitable for acetyl cellulosewhich comprises coupling a diazotized solution of aniline withm-anisidine.

6. A dyestuff suitable for dyeing acetyl cellulose which has thefollowing formula:

(SCH;

'7. A process of preparing a dyestufi suitable for acetyl cellulosewhich comprises coupling a diazotized solution of p-anisidine withaminohydroquinone-dimethyl-ether.

8. A dyestufi suitable for dyeing acetyl cellulose which has thefollowing formula:

OCH;

EW MMQNH.

9. A process for producing azo dyes which comprises coupling diazotizedaniline with aminohydroquinone-dimethyl-ether.

10. An azo dye having the following formula:

OCH;

HENRY JORDAN. MLES AUGUSTINUS DAHLEN.

